WO2007055070A1

WO2007055070A1 - Oil-based ink composition for writing utensil and writing utensil employing the same

Info

Publication number: WO2007055070A1
Application number: PCT/JP2006/319086
Authority: WO
Inventors: Shuji Ichikawa
Original assignee: Mitsubishi Pencil Co., Ltd.
Priority date: 2005-11-11
Filing date: 2006-09-20
Publication date: 2007-05-18
Also published as: EP1956057A1; US20090255439A1; US7794533B2; JP2007131776A; CN101305062A; CN101305062B; JP4698390B2; EP1956057B1; EP1956057A4

Abstract

An ink composition which contains an olefin wax dispersion added in order to enable the ink composition to give a smooth writing feeling and be free from insufficient ink transfer just after drawing initiation. This ink has significantly improved long-term stability. The oil-based ink composition comprises a solvent selected from the group consisting of monohydric alcohols, polyhydric alcohols, and glycol ethers, a colorant selected from the group consisting of pigments, dyes, and pigment/dye mixtures, and a resin, and is characterized by further containing a dispersion of reprecipitated olefin wax particles.

Description

Oily ink composition for writing instruments and writing instrument using the same

Technical field

The present invention relates to “oil-based ink compositions”, particularly “oil-based ink pens, oil-based ball pens” and the like. The present invention also relates to a writing instrument using such an oil-based ink composition.

Background technology

Wax is added as a compounding agent to be added to oil-based ink compositions such as writing instruments such as oil-based sign pens and oil-based ballpoint pens and desk supplies. Waxes are used in writing instrument inks for various purposes, taking advantage of their solubility and ability to form interfacial films. Such examples are disclosed in Kaihei 1 1-3 3 5 6 1 2, JP 2 0 0 1-2 4 0 7 8 8, and JP 2 0 0 3-2 1 3 1 6 2. And Japanese Patent Application Laid-Open No. 1-9-9270.

Japanese Patent Application Laid-Open No. 11-33 5 6 1 2 discloses that an oxide wax is used as an ink composition to prevent dry-up when left with the cap of the quick-drying oil-based marking van removed. It is described to be added to the product. The method for adding the oxidized wax to the ink composition disclosed in this publication is simply mixing.

Japanese Patent Laid-Open No. 2 0 3-2 1 3 1 6 2 describes that paraffin waxes are added to the correction fluid composition in order to prevent the pen tip of the writing tool type correction tool from drying. . The method for adding paraffin wax to the ink composition disclosed in this publication is that the paraffin wax is simply dissolved and then mixed with the correction liquid composition as it is. Is Umono.

Japanese Patent Application Laid-Open No. 1-9 9270 To improve writing feeling by using oil-based ink composition for ball pens with a melting point of 60 ° C ~ There is no specific method for adding 7-x in which is described.

Conventionally, when a wax substance is used for a writing instrument, including polyethylene wax, the oily ink composition is used in view of the existence of its interface film forming ability and the blending method for dissolving the wax. It was difficult to mix these cocoons uniformly.

In addition, depending on the presence of this interfacial film forming ability or the dissolved state of the wax, a wax film may occur at the gas-liquid interface of the ink which is being stored over time or due to the temperature difference of the surrounding environment, In addition, it may interact with the raw materials in the ink to produce a precipitate.Furthermore, the wax is poorly wetted with the ink solvent, so that the wax is powdered or waxed. There were many problems such as sedimentation. Disclosure of the invention

Normally, when wax is introduced into an oil-based ink composition, the wax forms a film. This film becomes a foreign substance for the ink composition. Accordingly, the ink is dispersed in the ink composition so as not to form a film. The various problems described above when using a wax-based material in an oil-based ink composition for writing instruments is due to the poor stability of the wax dispersion dispersed in this ink composition. That was Katsuta.

An object of the present invention is to include an olefin wax dispersion added to give a smooth writing feeling without producing a force thread at the time of writing. It is to provide an oil-based ink composition having a significantly improved stability over time.

As a result of diligent research to achieve the above-mentioned problems, the present inventor has found that these problems can be solved by an oil-based ink composition having the following characteristics, and has completed the present invention.

The present invention comprises a solvent selected from the group consisting of monohydric alcohols, polyhydric alcohols, and glycol ethers, pigments, dyes, and color materials selected from the group consisting of mixtures of pigments and dyes, and resins. Another aspect of the present invention is an oil-based ink composition characterized in that the oil-based ink composition further comprises a re-precipitated olefinic ink particle dispersion. This is a writing instrument using the oil-based ink composition of the upper arm. '

In the oil-based ink composition of the present invention, the blended olefinic wax particle dispersion is very stable, so that the wax film at the gas-liquid interface due to the difference in the temperature and temperature of the surrounding environment during ink storage. Since there is no generation of fee materials due to the interaction between the raw materials in the ink and the wax particles so that the generation is suppressed, the stability of the ink over time is greatly improved.

. In addition, the wettability of wax to ink solvent is good.

No fouling or sedimentation of fox. ,

Further, in addition to the above-mentioned advantages, the oil-based ink composition of the present invention can have the following effects by adding an olefin wax dispersion.

Improvement of writing ability (stickiness on writing up).

Suppression of ink adhesion (direct current) at the tip of the pen when the pen tip is down

Phenomenon that excessive ink adheres to or is transferred to the nib or stroke when writing Suppression (bothiness).

Also, unlike the case where wax particles are powdered in advance and added to a solvent or oil-based ink composition, they are precipitated in a solvent and directly granulated to form a dispersion. This is an advantage in manufacturing Niki.

In addition, the reprecipitated olefin waxes particle dispersion used in the ink composition of the present invention interacts with other components in the oil-based ink composition to cause aggregation and precipitation over time. It was unexpectedly found to function as an additive imparting appearance visibility because it is very stable. “Appearance visibility” means that the ink appearance color is the same as the ink stroke color. When the ink color material is a dye, the ink appearance color is usually a dark color that is almost black, and the ink appearance color looks very different from the ink drawing color, so the appearance visibility is very high. It will be in a bad state. Ink. Since the appearance color and the stroke color of the ink are relatively consistent (that is, to have “appearance visibility”), white emulsion and particles are generally used as an additive. However, this method has many problems when an intermediate polar solvent is used as the ink ^ agent. In the oily ink composition of the present invention, It has the advantage of having good appearance visibility even without using a specific additive for imparting appearance visibility. Best Mode for Carrying Out the Invention

The polyolefin-based ink that can be used in the oil-based ink composition of the present invention is a hook having a dropping point of 70 to 200 ° C. Here, the dropping point is the temperature at which wax begins to drop when it is heated in a specified container and becomes liquid at high temperatures. Specific examples of polyolefin waxes include polyethylene wax, Examples include polypropylene wax, low molecular weight ionomer wax, and polytetrafluoroethylene wax. Particularly preferred polyolefin waxes are polyethylene wax and polypropylene wax.

Specific examples of the polyethylene wax that can be used in the present invention include, for example, 3 0 2 0 0 B (ethylene butene copolymer), 2 2 0 3 A, 1 1 0 5 4 5 1 9 2 BA (carboxylic acid-modified ethylene butene copolymer) and HW 2 6 5 0 2 PE (oxidized type ethylene propylene / lene copolymer) and A—C manufactured by Honey Wei 1 6 and 6 A, A—C 8 and 8 A, A _ C 9 and 9 A, A _ C 6 Γ 7 and 6. 17 A, and A—C 6 2 9 and 6 2 9 A. A specific example is Neowax LA (melting point: 105 ° C.) manufactured by Yashara Chemical Co., Ltd.

In addition, polar waxes are introduced by oxidation treatment, or acrylic acid copolymerization, vinyl acetate copolymerization, oxidative copolymerization, or maleic anhydride copolymerization, polyethylene wax and Polypropylene wax is also preferred. .

The polyolefin-based ux dispersion obtained by the dispersion rest preparation procedure according to the present invention has a dispersed particle diameter of 10 ηπ! ~ 50 m.

The nonpolar medium for dissolving the olefinic wax used in the oil-based ink composition of the present invention satisfies the following conditions in consideration of the subsequent precipitation process.

(1) a medium that is compatible with the olefin wax at a temperature between 60 and 25

(2) Medium compatible with solvent having glycol etheric hydroxyl group (3) a medium in which the solubility of the polyolefin-based box is 10% by mass or less at a temperature of 0 ° C. or higher and 50 ° C. or lower; and

(4) A medium having a boiling point of 1550 ° C or higher.

The medium compatible with the olefin wax at a lower temperature of 60 ° C may dissolve the olefin wax even in a normal indoor environment, and the medium compatible with the temperature higher than 25.0 ° C. Considering the operation of re-precipitation to form particles and the nature of the solvent used as the dispersion medium, it is too hot and dangerous. In addition, when this medium is compatible with a solvent having an alcoholic hydroxyl group, which is an intermediate polarity solvent, the non-polar medium is easily transferred from the precipitated particles to the solvent in the subsequent precipitation step. The condition that the solubility of the olefinic wax is 10% by mass or less at a temperature of 0 ° C. or more and 50 ° C. or less is that when the re-precipitation particles are formed, it is difficult to dissolve the wax. This is to facilitate particle formation.

Furthermore, it is desirable that the boiling point of the medium is 1550 ° C or higher in order to ensure operational safety when dissolving the olefin wax.

Examples of non-polar media that can be used in the writing instrument dispersion of the present invention are:

,

Monoterven solvent or liquid terno resin. The terpenes are preferably monoterbenos that are liquid at room temperature. The monoterpene may be either a cyclic monoterpene or an acyclic monoterpene. Specific examples of the monoterbene solvent include the following. Pinene (bicyclic monoterpene) For example, Yasuhachira Chemical

,

Brand names made by the company: pinepine and 3_pineno, myrcene (acyclic monoterpenes), limonene (monocyclic monoterpenes), for example, the product name D — Limonene N, manufactured by Yasuharakemiruru Terpinolene (monocyclic monoterpene), for example, Yasuhara Chemical's trade name Yuichi Pinoren Cineol (bicyclic monoterpene), for example, the brand name Cineol D and Cineol C, manufactured by Yasuhara Chemical Co., Anethole (monocyclic monoterpene), for example, the brand name manufactured by Yasuhara Chemical Co., Ltd. G and anetor U, tervineol (monocyclic monoterpene), for example, Yasuhara Chemical's trade name Yuichi vineol, Perilla oil

(Monocyclic monoterpene), for example, trade name Pella Oil manufactured by Yasuhara Chemical Co., Ltd. Examples of liquid terpene resins include the product name Daimaron (terpene low polymer), the product name dimer resin (modified terpene low polymer), and the product name YS Oil DA (terpene low polymer) manufactured by Yashara Chemical Co., Ltd. Can be mentioned. '-

In addition to the above examples, n-Bomeo 1> d 1 -Camphor, I-Carveol, I-Carvy 1 acetate, Caryophy 1 ene, Caryopyl 1 ene oxide, manufactured by Nippon Terpene Chemical Co., Ltd. 1, -Cineole, 1, 8-C i neo 1 e, C it rone 11 al, IC it ronco 1, -Cymene, d-DihydrocarveoK I-Dihydrocarveo 1, d-Dihydrocarvone d-Dihydrocarvyl ace tate, ID ihyd rocarvy 1 acetate, Dihydroterpineol Dihydrotefpinyl ace ta te.Dimal H, E 1 emene, Eugeno 1,-Famesene, I soborny 1 acetate, I soborn y 1 eye 1 ohexano 1, dL imonene, IL imonene, dL imonene oxide, I-Limonene oxide, Linalool oxide f urano id, Linalool ox i de py ranoid, p-Menthane, I-Menthol, I-Men thone, β -Myrcene, Myrte na K Myr tenol, My rt eny 1 acetate, I-per i 1 lyl alcohol, I I P'eril lyl acetate, 3-0ctanoK 3-0c ty 1 acetate, I-Pcr i 11 a 1 dehyde, -P i nene, β -P inene, a -P inene oxide, d—Puregone, d 1- Rose o xide, Sobrerol, -Terpinene, r -Terpinene, Terpineol a-Te rp i neo K I- -Terpineol> 4-Ter pineol> Terpinolene, -Te rp i ny 1 ace tate, Ve rbeno 1, Verbenone, 3-Carene, Carane oxide, T e ruso 1 ve DTO-210, Terusolve THA-90, Terusolve THA-70, Terpin yloxy e thano 1, Dihydroterpinyloxy e thano 1, Terpinyloxy me thy lether, Dihydroterpinyl me thy 1 e the r, etc. And other products based on these.

The solvent that can be used for precipitating the wax particles from the medium in which the olefin wax is dissolved is a solvent selected from the group consisting of monohydric alcohols, polyhydric alcohols, and glycol ethers. In particular, those having a boiling point of 70 or more are preferred. This is to avoid handling hazards during manufacturing operations.

Examples of monohydric alcohols are aliphatic alcohols having 2 or more carbon atoms, such as ethanol, n-pronool, isop-butanol, η-butanol, and isobutanol. , Tert —butyl alcohol, 1 —Pen Yunol, isoamyl alcohol, sec —Amyl alcohol, 3 —Pen Yunol, ter r. T —Amyl alcohol, n _hexanol, methylamyl alcohol, 2 — Ethylbu Yunol, n-Hep Yunol, 2_Hep Yunol, 3—Hep Yunol, n—Octanol, 2 —Oct Yunol, 2 —Ethylhexanol, 3, '5, 5 — Trimethyl Hexanol, Sonanol, n-decanol, Undecanol, Trimethylnonyl alcohol, Tetradecanol, Heppu decanol, Cyclohexanol, 2-Methylcyclohex Examples include sanol and various other higher alcohols.

Polyhydric alcohols include ethylene glycol, ethylene glycol, 3-methyl-1,3-butanediol, triethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1, Examples thereof include polyhydric alcohols having 2 or more carbon atoms and 2 or more hydroxyl groups in the molecule, such as 5-pentanediol, hexylene diol, and octylene glycol. For example, methyl isopropyl ether, ethyl ether, ethyl propyl ethere, ethyl butyl ether, isopropyl ether, butyl ether, hexyl ether, 2_ ethyl hexyl ether, Ethylene monoethyl ether, ethylene glycol mono-2-ethyl butyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether , Ethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, 3 methyl-3-methyl ― 1 —Butanol, 3 _Methyl-1-Butanol, P P-Pyrengcol monomethyl ether, P □ Pyreneglycol monoethyl ether-Tell, Propylene glycol Monop Tert-butyl ether, dipropylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dibu □ pyrene glycol monobutyl ether, tripropylene glycol monomethyl ether,卜 U propylene dallic monobutyl ether, teraburopyrene U col monobutyl ether, etc.

Particularly preferred is a solvent as shown in the following chemical formula 1. Chemical formula 1: [Chemical formula 1]

(In the formula, R ′, R ² and R ³ are each independently H or CH _3. ) ■ As a solvent having the chemical formula (1), for example, puffer pyreno, glycol monomethyl ether, 1, 3 years old, 3 years 1

-Butanol, 3 -Methyl-3 Monomethyl-1 Monobutanol, etc.

A dispersing agent can be used when precipitating the refining series used in the oil-based ink composition of the present invention in a solvent to form particles or dispersing it. Such dispersants are in particular surfactants or polymer resins.

Preferred surfactants have polyoxyethylene (POE) or polyoxypropylene in the molecule in repeating units of 5 to 300, or are repeated using polyoxyethylene and polyoxypropylene in the molecule. It is a polymer substance having units 5 to 300.

Specific examples of surfactants that can be used as dispersants include sorbene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbite 卜 fatty acid esters, glycerin, Polyglycerin fatty acid esters and acetates, Propylene glycol fatty acid esters, Ethylene oxide derivatives of glycerin propylene glycol fatty acid esters, Polyoxyethylene alkyl ethers, Polyoxyethylene polyoxypro Pyrene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene castor oil / hardened castor oil derivatives, lanolin / beeswax derivatives, polyoxyethylene alkylamines and fatty acid amides, and derivatives thereof A commercially available product may be used.

When the surfactant is added, the amount is not more than twice the mass of the olefinic wax used to form the wax particles.

When a polymer resin is used as a dispersing agent, it is a polymer resin that dissolves 5% or more at 25 in the solvent for precipitating 7-axle particles. Preferred polymer resin is soluble in glycomonoether in an amount of more than 10% by weight, cane resin, styrene resin, styrene-alkyl resin.

Terpene phenol resin, oral gin modified maleic resin, □ gin phenol resin, alkyl phenol resin, phenol resin, styrene maleic resin, rosin resin, acrylic resin, urea aldehyde resin And resins represented by maleic acid-based resins, cyclohexanone-based resins, polyvinyl butyral, polyvinylpyrrolidone, and the like. Among these, particularly preferred polymer resins are styrene-acrylic resin, ketone resin, maleic acid resin and phenolic resin. When the polymer resin is added, the amount thereof is equal to or less than the same amount as the mass of the polyolefin-based ox used to form the ox particles.

Examples of the preparation of an olefin wax dispersion used in the oil-based ink composition of the present invention include an olefin wax for forming wax particles having a dropping point of 10 ° C. or more, such as polyethylene Prepare a polypropylene wax and heat it to a temperature range of 70 to 160 ° C with a non-polar medium, for example a liquid terpene resin. The solid wax is dissolved by stirring. The solution is cooled to 70 ° C to 100 ° C. In the same way, a solvent compatible with darlycol ether heated to 70 to 100 ° C, such as 3-methoxy, 3-methyl, 1-butanol, is added to this wax solution. Add gradually. At this time, a predetermined amount of the surface coating dispersant PE (5) alkyl alcohol is dissolved beforehand in 3-methoxy, 3-methyl, 1-butanol. When this solvent is gradually added to the wax solution, the dissolved olefinic wax precipitates in 3-methoxy, 3-methyl, 1-butylol and forms particles, resulting in a dispersion. Allow it to cool down and continue stirring while lowering the temperature. The surface coating dispersant POE (5 :) alkyl alcohol can also be added at this time. The olefin series dispersion can be obtained by the above procedure. The solvent used in the oil-based ink composition of the present invention is the same type as the solvent used to prepare the wax dispersion. Therefore, the ink solvent used in the oil-based ink composition of the present invention is a solvent selected from the group consisting of monohydric alcohols, polyhydric alcohols, and darlycol ethers. As the ink solvent, a solvent selected from the group consisting of monohydric alcohols, polyhydric alcohols, and glycol ethers can be 50 to 100% by mass with respect to the total amount of ink, and this is the main solvent. It is. The solvent used in the ink composition of the present invention is a solvent having a vapor pressure of not less than 0.0 0.1 mm Hg at 25, more preferably not less than 0.1 mm Hg. is there.

If the vapor pressure of this solvent is too low, it will be used as an oil-based ink composition, and problems such as stroke dryness and back-through will occur when written on paper. If the vapor pressure is too high, the solvent will evaporate from the tip of the pen when used as a ballpoint pen ink, resulting in poor initial writing and inability to write. Also

Even if an ink follower is placed at the rear end of the pen to prevent direct volatilization, Over time, the solvent permeates the ink following ability and the ink properties change.

In the pole pen using the oil-based ink composition of the present invention, when the above-mentioned preferred solvent is used, such a problem does not occur, but the ink solvent completely evaporates from the rear end of the pen. In order to suppress and further suppress the absorption of the ink agent, it is preferable to fill the ink follower to the rear end portion of the ink refill. Specific examples of solvents that can be used in the oil-based ink composition of the present invention are the same as those described in the section of the urethane wax dispersion.

These solvents are preferable from the viewpoint of the performance, safety, oral toxicity, etc. of the oil-based ink composition related to the vapor pressure of the solvent. -The dye used in the oil-based ink composition of the present invention is used in general oil-based ink compositions as long as the dye used does not destroy the olefin wax dispersion. Any dye can be used.

Examples of these dyes include direct dyes, acid dyes, basic dyes, mordanting / acidic mordant dyes, liquor, soluble dyes, azoic dyes, sulfurization / sulfurization used in ordinary dye ink compositions. Arbitrary dyes, vat dyes, disperse dyes, oil-soluble dyes, food dyes, metal complex dyes, salt-forming dyes, dyes dyed on resins, and the like can be used. Among these, a salt-forming dye, a dye obtained by dyeing a resin, and the like are preferable. The blending amount of the dye can be in the range of 1 to 50% by mass based on the total amount of ink.

Examples of salt-forming dyes used in general oil-based ink compositions include Paris First Color (registered trademark, manufactured by Orient Chemical Industry Co., Ltd.), Eisen Spiro Dye, Eisen SOT Dye (registered trademark name). Hodogaya Chemical Industry Co., Ltd.). For dyes dyed on resin, keiko—C o 1 ot

M P I — 5 0 0 series, k e i k o one C o 1 o t M P I-5 0

0 C series, k e i k o — C o 1 o t N S _ 1 0 0 0 There is a series.

In addition to the dispersion and the dye, the oil-based ink composition of the present invention can be added with a colorant for improving the writing performance of the ball vene, the effect of Kizuki, a surfactant, an auxiliary solvent, etc. Furthermore, it is possible to add an antifungal agent, an antifungal agent, a lubricant, a wetting agent, etc. that can be compatible without adversely affecting the oil-based ink composition. -As the auxiliary solvent, not only aliphatic solvents but also aromatic solvents can be used. In particular, benzylyl alcohol and ethylene tert-monophenyl ether are effective as a dye-dissolving aid, and therefore may be preferable to use as a co-solvent.

Specific examples of the writing instrument of the present invention include oil-based sign pens and oil-based ballbens. In the case of an oil-based ballpoint pen, it is composed of a ball, a tip of a tip holder, an ink receiving tube, a joint connecting the tip and the receiving tube, a pen shaft, and the like. It can be filled with objects.

When the ink composition of the present invention is used as a ballpoint pen ink, it is preferable to provide an ink follower to the rear end of the ballpoint pen refill. Since the solvent used is volatile, it prevents volatilization and moisture absorption.

This is because the ink follower is effective for preventing ink leakage. Example

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. All percentages shown in the examples are mass%. Reprecipitation used for ink preparation The olefin wax particle dispersion thus prepared is prepared in advance and sealed in a glass bottle.

(Examples 1 to 40) and (Comparative Examples 1 to 32) are as described below. In addition, in the following examples, a predetermined amount of each of the reprecipitated olefin wax particle dispersion and the evaluation ink composition is added and mixed in a constant temperature bath of 40 ° C. or higher to obtain the final ink composition. It was.

<Sodium-precipitated olefin wax particle dispersion— 1> olefin wax: AC-9A

Soluble wax solvent: YS oil DA-Glycol ether compatible solvent: 3-Methoxy,

3 -methyl

Dispersant for surface coating: P0E U0) lanolin alcohol

A re-deposited olefin wax particle dispersion 1 was prepared by the following procedure.

A predetermined amount of olefin wax A C—9 A and a medium Y S oil D A for dissolving this olefin glass is placed in a container. This is heat-stirred in the range of 7 to 160. Then, cool and adjust the temperature to about 70 to 100 ° C. Then, a solution obtained by dissolving a predetermined amount of dispersant PE (40) lanolin alcohol in Solvent 3-Methyl, 3-Methyl, 1-Butanol and heating to 70-100. When the olefin wax is gradually added to this ox solution, the dissolved olefinic wax precipitates in 3-methoxy, 3-methyl, 1-bubutol and is granulated to obtain a dispersion. Further, stirring was continued while allowing to cool by lowering the temperature to obtain an olefin wax dispersion of the present invention.

In the following, dispersions 1-2 to 10 were used with various polyolefin waxes, and the procedure described in <Reprecipitated polyolefin wax particle dispersion 1> was repeated to repeat the reprecipitation of the present invention. Wax A particle dispersion (wax dispersion) was prepared. The composition of the dispersion used in each example is described below.

<Re-deposited olefin wax particle dispersion-2>

Olefin wax: AC-629 7.0¾ Olefin wax dissolution medium: a-Limonene 12.0¾ Olefin wax dissolution medium: Isoborny 1 eye lohexanol 8.0 Solvents compatible with glycol ether: 3-Methoxy,

3-methyl, bububutanol 71.0% Dispersant for surface coating: P0E (40) lanolin alcohol .. 2.0¾ re-precipitated olefinic particle dispersion _ 3>

Olefin Wax: 45192BA 3.0¾ Solvent Wax Solvent: YS Oil DA 20.0% Solvent compatible with glycol ether: 3-Methoxy,

3-Methyl, Nylbutanol 76.0% Dispersant for surface coating: P0E (15) octylphenol 1.0¾

<Re-deposited olefin wax particle dispersion 4>

Olefin Wax: AC-597, 8.0% Solvent Wax Dissolving medium: YS Oil DA 25.0¾ Solvent compatible with glycol ether: 3-Methoxy,

3-methyl, 卜 butyl alcohol ■ 60.0% Dispersant for surface coating: P0E (20) POP (8) Cetyl ether 7.0%

<Re-precipitated olefin wax particle dispersion 5>

Olefin wax: AC-8A 5.0% Olefin wax dissolution medium: P-Menthane 5.0¾ Olefin wax dissolution medium: Isobornyl cyclohexanol 10.0% Solvent compatible with glycol ether: 3-methoxy,

3-methyl, 卜 buyuol 77.0% Dispersant for surface coating: POE (4) oleyl ether 3.0¾

<Re-deposited olefin wax particle dispersion rest— 6>

Olefin wax: Neowax LA05 4.0% Olefin wax dissolution medium: YS Oil DA 18.0¾ Solvent compatible with glycol ether: 3-Methoxy,

3-methyl, 卜 buenoluol '74.0% Dispersant for surface coating: P0E (23) Lauryl ether' 4.0% reprecipitated olefin wax particle dispersion — 7>

Olefin wax: AC-629, 5.0% Olefin wax dissolution medium: Dihydroterpinyl acetate 25.0% Solvent compatible with glycol ether: 3-Methoxy, ■ '.

3-Methyl, Nylbutanol 68.0¾ Surface coating dispersant: P0E (5) Lanolin alcohol 2.0¾

Olefin wax: HW26502PE 8.0% olefin wax dissolution medium: YS oil DA 25.0% Solvent compatible with glycerol ether: 3-Mexoxy, '

3-Methyl, 卜 butyl alcohol 65.0% Dispersant for surface coating: Polyvinyl petital 2.0% reprecipitated olefin wax particle dispersion 9

Olefin wax: AC-597 5.0% Olefin wax dissolution medium: YS oil DA 25.0¾ Solvent compatible with glycol ether: 3-methoxy,

3-methyl, 卜 butanol 68.0% Dispersant for surface coating: P0E (15.2) 卜 Rebenzyl phenyl ether 2.0%

<Re-deposited olefin wax particle dispersion 1 0>

Olefin wax: 2203A 8.0¾ Olefin wax dissolution medium: YS Oil DA

Solvents compatible with glycol ether: 3-methoxy,

3 -methyl

Surface coating dispersant: Resin SK

1 1〉 For the comparative example,

Olefi, N-type wax: Solvent compatible with glycol ether in the form of powder without dissolving neowax LA 0 5: Dispersed in 3—Methoxy, 3—Methyl, 1_Buvenol Were prepared.

The obtained dispersion is charged in the form of powder without dissolving the wax-based wax having the same composition as that described in the section 6>. Therefore, no olefin wax dissolving medium or surface coating dispersant is used.

<Wax reprecipitation particle dispersion other than olebuin type 1 2> For comparative example

Wax: Castor oil wax system D I SPALON 4300 8.00¾ Wax dissolution medium: YS oil DA 25. 0% Glycol ether compatible solvent: 3-methoxy,

3-Methyl, butyl alcohol 60.0% Surface coating dispersant: P0E (5) Lanolin alcohol 7.0%

<Wax reprecipitation particle dispersion other than olefin-based 1 13> For Z comparative example

Wax: Castor oil wax system D I SPALON305 8.0% Wax dissolution medium: YS oil DA 25.0% Solvent compatible with Dalicol ether: 3-Methoxy,

3-methyl, 卜 butyl alcohol 67. 0¾ Non-guarffinic wax reprecipitation particle dispersion 1 4> For comparative example

The same operating procedure except that the olefin wax AC-9A used in <Reprecipitated olefin wax particle dispersion-1> was replaced with a modified amide wax and no surface coating dispersant was used. A dispersion was prepared.

Wax: Modified Amidox D I S.PAL0N6650, 5.0 Wax dissolution medium: YS oil DA 25.0 ¾ Solvent compatible with glycol ether: 3-methoxy,

3-methyl, bububutanol 70.0¾ Wax reprecipitation particle dispersions other than guanefin 1 δ> κ For comparative examples

Except that the olefin wax AC 19 A used in <Reprecipitated olefin wax particle dispersion 1> was replaced with a amide polyethylene polymer and no surface coating dispersant was used. Dispersions were prepared using the same procedure.

Wax: Amide / Polyethylene system D I SPALON F-9050

5. 0¾ Wax dissolution medium: YS Oil DA 25. 0% Solvent compatible with Glycol Ether: 3

3-Methyl, 卜 Buunol 70. 0¾

<Re-precipitated olefinic particle dispersions-16> / for comparative examples

<Re-precipitated olefinic particle dispersion 1> olefin wax was changed to LA05, which is the olefinic solvent, and the solvent 3—methoxy, 3-methyl, 1 A dispersion was prepared using the same procedure except that the kanol was changed to xylene. Olefin Wax: Neo Wax LA05 5.0% Olefin Wax Dissolving Medium: YS Oil DA 25. 0¾ Solvent: Xylene 68.0 0¾ Surface Coating Dispersant: P0E (5) Lanolin Alcohol 2.m Precipitated olefin wax particle dispersion 1 17> For comparative example.

<Re-precipitated olefin wax particle dispersion-1> The olefin wax of 1> is changed to the olefin wax 30 0 0 0 B, and the wax dissolution medium YS oil DA is changed to polypro and pyrendicol. A dispersion was prepared by the same operation procedure except that it was changed.

Olefin wax: 30200B 5: 0¾ Olefin wax dissolution medium: Polypropylene glycol

(Molecular weight 400) 25. 0¾ Solvents compatible with Daricol ether: 3-methoxy,

3-Methyl, Nylon benzene. 68. 0¾ Surface coating dispersant: P0E (5) Lanolin alcohol 2.0

<Reprecipitated olefin wax particle dispersion— 1 8> / ^{/ For} comparative example

No olefin wax reprecipitated particle dispersion was added, and 5% by weight of 3-methoxy, 3-methyl, 1-butanol was added.

The evaluation ink composition to be mixed with the wax particle dispersion had the following composition.

Spiron Biolet C-RH [Hodogaya Chemical Co., Ltd.

Spiron erotic C-GNH [Hodogaya Chemical Industry:

P r i n t ex # 35 [Degussa]

Polyvinyl petitlar BL-1 [manufactured by Sekisui Chemical] High rack 110H [manufactured by Hitachi Chemical]

GWIS-125 [Nippon Emulsion made

3-methoxy, 3-methyl, 卜 butanol

Spiro Blue C-RH [Hodogaya Chemical Co., Ltd.] Spiron Biolet C-RH [Hodogaya Chemical Co., Ltd.] Kumo Mophthal Blue A-3R [Ciba-Gaigi Co., Ltd.] Polyvinyl Petitral BL-1 [Sekisui Chemical Co., Ltd.]

High rack 110H [Hitachi Chemical Co., Ltd.]

Oleic acid

Ethylene glycol monophenyl ether

3-methoxy, 3-methyl, 卜 butanol

Ink composition for evaluation— '3>

Spiron Biolet C-RH [Hodogaya Chemical Industry: Kuguchi Mophthal Violet Β [Ciba Geigy Co., Ltd.] Polyvinyl Petitral BL-S [Sekisui Chemical Co., Ltd.]

High rack U0H [manufactured by Hitachi Chemical]

Ethylene glycol monophenyl ether

3-Methoxyb Yunol

3-Methyl; 3-methyl, 卜 butanol

Spiro Violet C-RH [Hodogaya Chemical Co., Ltd .: Spiro Yellow C-GNH [Hodogaya Chemical Co., Ltd .: Pr intex # 35 [Degussa Co., Ltd.] Polyvinyl butyl, tilal BL-1 [Sekisui Chemical Co., Ltd.]

High rack 110H [manufactured by Hitachi Chemical]

3-Methoxyb Yunol 3-Methoxy, 3-methyl, 卜 butanol 60.0% Add the dispersions of the inventive examples and comparative examples to these evaluation ink compositions to create the final ink compositions and implement them. Examples 1 to 40 and Comparative Examples 1 to 3 2 were used. The blending amount for making the final ink composition is as follows.

Hacks particle dispersion: 5% by weight

Ink composition for evaluation: 95% by weight.

Please refer to the table below for the evaluation results of various ink compositions for evaluation and combinations of Invention Examples and Comparative Example Dispersions.

In the examples and comparative examples, the ink obtained as described above was filled and the following evaluation test was performed. '.

The ball-point pen used in the test has a 1.6 mm inner diameter polypropylene propeller tube and a stainless steel tip (the ball is a cemented carbide alloy with a diameter of 1.0 mm). Further, after filling, the sample was allowed to stand for 30 minutes under conditions of 25 ° C. and 65%, and the following evaluation was performed.

1) Scratch evaluation at the time of writing (Sensory evaluation)

The letters “MITSUBISHI” were written, and the strength of these letters was judged using the following criteria.

There is almost no blur (no blur after the second line of “M”); 〇 ',

A little more (the letters after “B” are not blurred) △

Excessive amount (because of damage, "MITSUBISHI" cannot be written to the end); X

It was.

2) Scratch evaluation at the time of writing (machine evaluation)

Set the pen at an angle of 60 ° under the condition of 2 5 at 65%, apply a load of 20.0 g, move the contacting paper at a speed of 2 mZmin, Written lines were observed. At that time, measure the distance from the starting point to the drawn line where writing started. Five pens were prepared, and the average value was calculated as the measured value.

In order to observe long-term smearing, the standing period after filling was set to 1 day.

Measured value ≤ 50 mm: ○ '

Measured value ≤ 1 0 0 mm: △. '1 0 0 mm <Measured value: X

It was. -

3) Writability evaluation Line breakability (sensory evaluation)

Using PPC paper at room temperature, we observed the degree of cracking of the drawn lines when writing continuously in a spiral shape (the part where ink was not transferred during writing), and judged using the following criteria.

Slightly non-breaking, Slightly cracking, 〇 Slightly more cracking, △

Very many line breaks; X

It was. '

4) Low-temperature stability · Writability evaluation Z-ray cracking (sensory evaluation)

Left in an ambient environment at 0 ° C for 3 days. One hour after removal, at room temperature, observe the degree of line cracks in the wrinkles drawn in a spiral shape continuously using PPC paper (the part where ink does not transfer during writing) and use the following criteria: Judged.

Those that hardly break or are only slightly broken;

Yes

Slightly broken line △

Very many line breaks; X

It was. 5) Low-temperature stability · Ink gas-liquid interface and sediment evaluation (Sensory evaluation) The prepared ink composition is sealed in a 20 ml glass bottle and stored, at 0 ° C and 5.0 ° C. And left for 12 weeks in a thermostatic layer changing in a 12-hour cycle. After removal, visually observe the generation of foreign matter on the gas-liquid interface, and stir the generation of sediment with a metal spatula so that the lower part is scooped. Judgment was made using criteria.

〇 No wrinkles, no foreign matter or sediment on the gas-liquid interface; 〇

Slight foreign matter or sediment on the gas-liquid interface can be confirmed; Δ. Foreign matter or sediment on the gas-liquid interface can be clearly confirmed; .

These evaluation results are shown in the following table.

Table showing evaluation results

Note). Comparative Example 7, 1 5. 23, 3 1;

At the stage of dissolving the wax, it became poor in fluidity and could not be prepared as a redispersion. As is apparent from these results, the ink compositions of Examples 1 to 40 that are within the scope of the present invention are compared with the ink compositions of Comparative Examples 1 to 32 that are outside the scope of the present invention. Excellent blurring at the time of writing, excellent writing with a soft and smooth handwriting, and excellent It was found that line breakage during writing was greatly improved due to the stability of the ink over time. ,

Therefore, according to the present invention, unlike the conventional method, the writing blur is suppressed at the time of writing, it is excellent in making the handwriting soft and smooth, and the ink is stable over time. An ink composition for ballpoint pens is provided that makes it possible to significantly improve line breakage at the time. ,

Claims

The scope of the claims

1. a solvent selected from the group consisting of a monohydric alcohol, a polyhydric alcohol, and a darlycol ether, a coloring material selected from the group consisting of a pigment, a dye, and a mixture of a pigment and a dye, and a resin. An oily ink composition comprising:

In addition, an oil-based ink composition comprising a re-precipitated olefin-based wax particle dispersion.

2. The blending amount of the reprecipitated olefin wax particles dispersion is from 0.01 to 30% of the total mass of the ink composition as the solid content of the olefin wax. The oil-based ink composition according to claim 1, wherein the oil-based ink composition is%.

3. The re-precipitated polyolefin-based particle dispersion is once

The olefinic wax is dissolved in a nonpolar medium that can dissolve or dissolve the olefinic wax between 60 ° C and 25 ° C, and then precipitated in the solvent. The oil-based ink composition according to claim 1, wherein the oil-based ink composition is obtained by

4. The oil-based ink composition according to claim 3, wherein the non-polar medium is selected from monoterpene solvents X selected from liquid terbene resins.

5. The solvent has a vapor pressure of not less than 0.001 mm Hg at 25 ° C. and accounts for not less than 50% by mass of the total solvent in the ink composition. The oil-based ink composition as described in any one of -4.

6. The oily property according to claim 5, wherein the solvent has a vapor pressure of not less than 0.1 mm Hg at 25 and occupies 50% by mass or more of the total solvent in the ink composition. Ink composition.

7. The structural formula (1) where the solvent is shown below:

(In the formula, RR ² and R ³ are each independently H or CH _3. )

The oil-based ink composition of Claim 5 or 6 represented by these.

8. A writing instrument using the ink composition according to any one of claims 1 to 7.